1,3,4-thiadiazolylazo-3-(cyclohexylamino)acylanilide dyes

ABSTRACT

Monoazo compounds having a 1,3,4-thiadiazolyl diazo component and a 3-(cyclohexylamino)acylanilide coupling component are useful for dyeing nylon and polyester textile materials on which the compounds exhibit improved properties such as excellent dyeability, lightfastness and migration on polyamide fibers and excellent resistance to sublimation on polyester fibers.

nited States Patent Weaver et al.

[ June 27, 1972 [54] 1,3,4-THIADIAZOLYLAZO-3- (CYCLOHEXYLAMINO)ACYLANILIDE DYES [72] lnventors: Max A. Weaver; James M. Straley; William H. Moore, all of Kingsport, Tenn.

[73] Assignee: Eastman Kodak Company, Rochester,

[22] Filed: June 16, 1969 211 App1.No.: 833,744

3,096,320 7/1963 Langeetal. ..260/158 3,221,006 11/1965 Moore et a1. ..260/158 2,286,795 6/1942 Dickey et a1... .....260/207.1 2,289,349 7/1942 Dickey et a1 ....260/207.1 2,289,376 7/1942 McNally et a1. ....260/152 2,683,708 7/1954 Dickey et a1 ..260/158 FOREIGN PATENTS OR APPLICATIONS 1,503,249 10/1967 France ..260/158 Primary ExaminerFloyd D. Higel Attorney-J. Frederick Thomson and Cecil D. Quillen, Jr.

[5 7] ABSTRACT Monoazo compounds having a 1,3,4-thiadiazolyl diazo component and a 3-(cyclohexylamino)acylanilide coupling component are useful for dyeing nylon and polyester textile materials on which the compounds exhibit improved properties such as excellent dyeability, lightfastness and migration on polyamide fibers and excellent resistance to sublimation on polyester fibers.

4 Claims, No Drawings 1,3,4-THIADIAZOLYLAZO-3- (CYCLOHEXYLAMINOMCYLANILIDE DYES This invention relates to certain novel monoazo compounds and, more particularly, to thiadiazolylazoaniline compounds in which the nitrogen atom of the aniline coupling component is substituted with a cyclohexyl group and a ring carbon atom of the coupling component is substituted with an acylamido group. This invention also concerns polyester and nylon fibers dyed with the novel monoazo compounds.

The novel monoazo compounds have the fonnula wherein R is halogen, alkanoylamido, alkylsulfonyl, R- or R- X- wherein R is an alkyl, allyl, cycloalkyl or aryl radical, and X is an oxygen or sulfur atom;

A is an acyl radical;

R is hydrogen, alkyl or alkoxy;

R is hydrogen or an alkyl radical;

R is lower alkyl; and

nisO, 1,2,01'3.

The novel azo compounds impart bright scarlet to pink shades on polyester and nylon textile materials. The compounds of the invention are unique in that they possess excellent properties when applied to either nylon or polyester fibers according to known dyeing techniques. For example, the azo compounds exhibit excellent dyeability, e.g. buildup and affinity, for and light-fastness on nylon fibers. The azo compounds also exhibit good migration properties on polyamide fibers and excellent resistance to sublimation on polyester fibers.

The alkyl radicals which R can represent can be straightor branch-chain, substituted or unsubstituted alkyl having from one to about carbon atoms. Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl and hexyl are typical of the uh.- substituted alkyl groups. Typical groups which can be present on alkyl radicals R are hydroxy, e.g. Z-hydroxyethyl, 3- hydroxypropyl; halogen, e.g. 2-chloroethyl, 3-bromopropyl; lower alkoxycarbonyl, e.g. Z-ethoxycarbonylethyl, 3-methoxycarbonylpropyl', lower alkanoyloxy, e.g. Z-acetoxyethyl; lower alkoxy, e.g. Z-methoxyethyl; lower alkanoyl, e.g. 2- acetylethyl; aroyl, e.g. benzoylrnethyl; cyano, e.g. 2- cyanoethyl; carbamoyl, e.g. Z-carbamoylethyl; dicarboximido, e.g. 3-succinimidopropyl; etc. As used herein to describe an alkyl moiety-containing group, lower designates a carbon content of up to about 4 carbon atoms. The alkyl radicals represented by R can also be substituted with cycloalkyl, e.g. cyclopentyl, cyclohexyl, cycloheptyl, and lower alkyl-substituted derivatives thereof, and with aryl, e.g. phenyl and phenyl substituted with lower alkyl, lower alkoxy, or halogen. Cyclohexylmethyl, 2-cyclopentylethyl, 4-ethylcyclohexylmethyl, 4-methoxycyclohexylrnethyl, 2-(3-chlorocyclohexyl)ethyl, benzyl, p-methylbenzl, 2-p-ethoxyphenylethyl, 4- chlorobenzyl, Z-phenylethyl, etc. are illustrative of the cycloalkylalkyl and arylalkyl groups which R can represent. The unsubstituted alkyl radicals which R can represent preferably are lower alkyl, e.g. methyl, ethyl, propyl, and butyl, while the preferred substituted alkyl radicals contain from about two to about eight carbon atoms, e.g. Z-hydroxyethyl, benzyl, cyclohexylmethyl, etc.

The aryl groups which R can represent preferably are monocyclie, carbocyclic aryl such as unsubstituted phenyl and phenyl substituted, for example, with lower alkyl, lower alkoxy, halogen, etc. The cycloalltyi groups represented by R include cyclopentyl, cyclohexyl, cyeloheptyl and lower alkylsubstituted derivatives thereof. Specific examples of the cycloalkyl and aryl groups which R can represent appear in the preceding paragraph. Chlorine and bromine are examples of the halogen atoms which R can represent. Examples of the alkanoyl moiety of the alkanoylamido groups represented by R and examples of the alkylsulfonyl groups which R can represent appear below in the definition of A. R preferably represents those groups having the formula R-X. Specific examples of the groups collectively represented by RX- e.g. alkylthio, alkoxy, arylthio, aryloxy, etc., are set forth in the examples of the novel azo compounds.

The acyl radicals represented by A can be formyl, lower alkanoyl, aroyl, cyclohexylcarbonyl, lower alkoxycarbonyl, aryloxycarbonyl, lower alkylsulfonyl, cyclohexylsulfonyl, arylsulfonyl, carbamoyl, lower alkylcarbamoyl, arylcarbamoyl, sulfamoyl, lower alkylsulfamoyl, furoyl, etc. The alkanoyl groups can be substituted with substituents such as halogen, aryl, cyano, lower alkoxy, benzyloxy, lower alkylthio, lower alkylsulfonyl, etc. The alkylsulfonyl groups also can be.substituted, for example with cyano, hydroxy, halogen and the like. The alkoxycarbonyl groups can be substituted, for example, with hydroxy, alkoxy and cyano. Acetyl, propionyl, butyryl, cyanoacetyl, chloroacetyl, trifluroacetyl, phenylacetyl, methoxyacetyl, methylthioacetyl, methylsulfonylacetyl, methoxycarbonyl, propoxycarbonyl, butoxycarbonyl, methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, 2- cyanoethylsulfonyl, 2-hydroxyethylsulfonyl, and 2- chloroethylsulfony], are examples of the alkanoyl, alkoxycarbonyl and alkylsulfonyl groups which A can represent. The aryl group, designated Ar, of the arylalkanoyl, aroyl, i.e. aryl- --carbonyl, aryloxycarbonyl, arylsulfonyl, and arylcarbamoyl groups preferably is monocyclic, carbocyclic aryl such as unsubstituted phenyl and phenyl substituted with, for example, lower alkyl, lower alkoxy, halogen, etc. Tolyl, anisyl, pbromophenyl and o,p-dichlorophenyl are typical of such aryl groups. Dimethylcarbamoyl, ethylcarbamoyl, propylcarbamoyl, butylcarbamoyl, phenylcarbamoyl and dimethylcarbamoyl are examples of the substituted carbamoyl groups.

Examples of the alkyl and alkoxy groups represented by R appear in the description relating to R. The alkyl group represented by R can be straightor branch-chain, substituted or unsubstituted alkyl of from one to about eight car bon atoms such as, for example, methyl, ethyl, isopropyl, propyl, butyl, isobutyi, l-methylbutyl, amyl, l,2-dimethylpropyl, l,3-dimethylbutyl, hexyl, Z-ethylhexyl, etc. Preferably, one of R and R is lower alkyl and the other is hydrogen. Lower cyanoalkyl, lower alkoxy-lower-alkyl and lower alkanoyloxy-lower alkyl are examples of the substituted alkyl groups represented by R. 2Cyanoethyl, 3-ethoxypropyl, 2- methoxyethyl, 2-propionoxyethyl, 2,3-diacetoxypropyl, etc. are examples of some specific substituted alkyl groups represented by R. Preferably, the unsubstituted alkyl groups represented by R are lower alkyl, the cyanoalkyl groups contain three or four carbon atoms, the alkoxyalkyl groups contain three to about six carbon atoms and the alkanoyloxyalkyl groups contain about four to about six carbon atoms.

The novel azo compounds which, because of their economy and, especially, their excellent properties, are particularly valuable dyes for nylon and polyester textile materials have the formula wherein R is lower alkyl, especially methyl or ethyl; X is and coupling the resulting diazonium salt with a coupler having the formula wherein R, R, A, R, R and n are defined above.

The diazotizable aminothiadiazoles are synthesized by techniques described in the literature (Ber. 28, 946; British Patent 726,045, J. Chem. Soc., 1967, 2,700-2,704). For example, 2-arnino-5-mercapto-l,3,4-thiadiazole can be treated with alkylating and arylating agents, such as alkyl halides, alkyl sulfates, alkyl phosphates, aryl halides, etc., at elevated temperatures in the presence of a solvent and a base such as potassium carbonate or sodium acetate.

The couplers can be synthesized by a variety of methods. For example, an acylamidoaniline or a nitroacyclanilide can be condensed with a cyclohexanone at elevated pressures and temperatures in the presence of a hydrogenation catalyst such as platinum to obtain the N-cyclohexyl-m-acylamidoaniline which, if desired, can be treated with an alkylating agent to yield the N-alkyl-N-cyclohexyl-m-acyla.midoaniline coupler.

The preparation of the couplers and the novel azo compounds of the invention is further illustrated by the following examples.

EXAMPLE 1 EXAMPLE 2 3-(Cyclohexylamino)acetanilide (11.7 g.), triethyl phosphate (15 ml.), and bromoethane (5.4 g.) are reacted on a steam bath for 6 hr. An additional 5.4 g. of bromoethane is added and the reaction is heated 4 hr. longer. The reaction mixture is drowned in water and ice. After the mixture is basified by the addition of Nl-LOH, the aqueous portion is removed by decantation. The product, 3-(N-cyclohexyl-N- ethylaminoyacetanilide, is recrystallized from 200 ml. methanol plus 400 ml. water. It melts at 88 to 90 C.

Analysis: Calcd. for C, ,0: C, 73.8; H, 9.3; N, 10.7.;

Found: C, 73.7; H, 9.3; N, 10.7.

EXAMPLE 3 A mixture of 3(cyclohexylamino)acetanilide (6.96 g.), acrylonitrile (5.3 g.), cuprous chloride (0.5 g.), and acetic acid (10 ml.) is heated at 90 to ll C. for 4.5 hr. The product is isolated by drowning in water and decanting ofl the aqueous layer. The product, 3-(N,2-cyanoethyl-N-cyclohexylamino)acetanilide, does not solidify readily but is pure enough to be used for preparing dyes.

EXAMPLE 4 A mixture of 3-arnino-p-acetotoluidide (16.4 g. cyclohexanone (24.7 g.), ethanol (50 ml.), acetic acid (2 drops), and 5 percent platinum on carbon catalyst (1.0 g.) is hydrogenated in anautoclaveat 165C. and 1,000psiuntilthehydrogenuptake ceases. The reaction mixture is filtered to remove the catalyst and the ethanol is removed by evaporation. The product, after being recrystallized from water-ethanol, melts at ll8to [19C. lthasthestructure:

NHCOCH:

EXAIMPLE 5 3-Amino-p-acetoanisidide (90.0 g.) and cyclohexanone 122.0 g.) are reacted as described in Example 4. The product 3-( cyclohexylamino )-p-acetoanisidide, after being recrystallized from ethanol, melts at 135 to 137 C.

EXAMPLE 6 To 5.0 ml. of cone. H 80 is added 0.72 g. NaNO, with stirring. The solution is cooled and 10 ml. 1:5 acid is added below 15 C. After cooling to about 3 C., 2-amino-5-ethylthio-l ,3,4- thiadiazole 1.61 g.) is added followed by 10 ml. of additional 1:5 acid at 0-5 C. After stirring for 2 hr. at 0 C., the diazonium solution is added to 3-cyclo-hexylamino-pacetotoluidide (2.46 g.) in ml. of 1:5 acid at less than 10 C. The coupling is bufi'ered by the addition of ammonium acetate and kept at about 5 C. for 2 hr. Water is added to precipitate the dye. The product is then collected by filtration, washed with water, dried in air, and recrystallized from methanol. The dye, which melts at 164 to 166 C., produces bright pink shades on nylon fabrics and has the structure:

NHCOCH:

EXAMPLE 7 2-Amino-5-methylthio-l ,3,4-thiadiazole 1.47 g.) is diazou'zed and coupled with 3-( N-cyclohexylamino )-pacetoanilide (2.32 g.) as described in Example 6 to yield 5-(N- cyclohexylamino)-2-( 5-methylthiol ,3,4-thiadiazol-2-ylazo acetanilide which imparts a pinkshade of excellent fastness to light to polyarnide fibers.

EXAMPLE 8 According to the procedure described in Example 6, 2- arnino-5-methylthio-l,3,4-thiadiazole (1.47 g.) is diazotized and coupled with 3-(cyclohexylamino)benzanilide (2.94 g.). The product, 5-(cyclohexylamino)-2-(S-methylthio-l,3,4- thiadiazol-2-ylazo)benzanilide, produces bright pink shades on polyarnide fibers.

EXAMPLE 9 The novel azo compounds can be applied to nylon and polyester textile materials according to known disperse dyeing techniques. Various dispersing and wetting agents can be employed in the dispersion of the finely divided dye compound in an essentially aqueous dyebath. Procedures by which the compounds of the invention can be applied to nylon and polyester textile materials are described in U.S. Pat. Nos. 2,880,050; 2,757,064; 2,782,187; 3,100,134 and 3,320,021. The following examples illustrate methods for applying the novel compounds to polyamide fibers and polyester fibers, respectively.

EXAMPLE 5 3 The azo compound (50.0 mg.) of Example 6 is dispersed in 5 cc. of 2-methoxyethanol. A small amount (3-5 cc.) of a 3 percent sodium lignin sulfonate solution is added, with stirring, and then the volume of the bath is brought to 150 cc. with water. A 5.0 g. textile fabric made of nylon 66 fibers is placed in the bath which is then slowly brought to the boil.

The dyeing is carried out at the boil for 1 hr. with occasional EXAMPLE 54 The azo compound of Example 8 (0.1 g.) is dissolved in 10 cc. of 2-methoxyethanol. A small amount (3-5 cc.) of a 3 percent lignin sulfonate aqueous solution is added, with stirring, and then the volume of the bath is brought to 300 cc. with water. 3 cc. of a solvent carrier (Tanavol) is added to the bath 7 and 10 g. of a textile fabric made of poly( ethylene terephthalate) fibers is placed in the bath and worked 10 min. without heat. The dyeing is carried out at the boil for 1 hr. The dyed fabric is removed from the dyebath and scoured for 20 min. at

C. in a solution containing 1 g./l. neutral soap and l g./l. 75

sodium carbonate. The fabric is then rinsed, dried in an oven at 250 F. and heat set (for removal of residual carrier) for 5 min. at 350 C. The polyester fabric is dyed a bright pink shade which exhibits excellent fastness tolight and resistance to sublimation when tested according to conventional AATCC procedures.

The compounds of the invention can also be applied to polyester textile materials by the heat fixation technique described in U. S. Pat. No. 2,663,612 and in the American Dyestuff Reporter, 42, 1 (1953).

As used herein, nylon textile materials" means fibers, yarns and fabrics having a basis of a synthetic linear polyamide such as nylon 66 (polyhexamethylene adipamide) manufactured by the polymerization of adipic acid and hexamethylenediamine, nylon 6 (polycaprolactam) prepared from epsilon-aminocaproic acid lactam (caprolactam), and nylon 8. A detailed description of the synthetic polyamide materials which are dyed bright fast shades by the compounds of the invention is set forth in U.S. Pat. No. 3,100,134. Polymeric linear polyester materials of the terephthalate sold under the trademarks Kodel, Dacron" and Terylene are illustrative of the linear aromatic polyester textile materials that can be dyed with the compounds of our invention. Examples of linear polyester textile materials that can be dyed with the compounds of the invention are those prepared from ethylene glycol and dimethylterephthalate or from cyclohexanedimethanol and dimethylterephthalate. Polyesters prepared from cyclohexanedimethanol and dimethylterephthalate are more particularly described in U.S. Pat. No. 2,901,446. Poly(ethylene terephthalate) polyester fibers are described, for example, in U.S. Pat. No. 2,465,319. The polymeric linear polyester materials disclosed in U.S. Pat. Nos. 2,945,010; 2,957,745 and 2,989,363, for example, can be dyed. The linear aromatic polyester materials specifically named have a melting point of at least 200 C. The poly(ethylene terephthalate) fibers which are dyed with the compounds of the invention are manufactured from a melt of a polymer having an inherent viscosity of at least 0.35 and preferably, about 0.6. The inherent viscosity of the poly-( 1,4- cyclohexylenedimethylene terephthalate) polymer is also at least 0.35. These inherent viscosities are measured at 25 C. using 0.25 g. polymer per ml. of a solvent consisting of 60 N H-A wherein R is phenyl; phenyl substituted with lower alkyl, lower alkoxy, chlorine or bromine; R-; or R"X; wherein R is lower alkyl; allyl; cyclohexyl; or cyclohexyl substituted with lower alkyl; and X is S or O;

A is lower alkanoyl; lower alkanoyl substituted with chlorine, bromine, aryl, cyano, lower alkoxy, benzyloxy, lower alkylthio, or lower alkylsulfonyl; lower alkoxycarbony]; lower alkoxycarbonyl substituted with hydroxy,

lower alkoxy or cyano; cyclohexylcarbonyl; each aryl group being phenyl, or phenyl substituted with lower a1- kyl, lower alkoxy, chlorine or bromine;

R is hydrogen or lower alkyl;

R is hydrogen or, when R is hydrogen, lower alkyl;

R is lower alkyl; and

nisO, l, 2or 3;

in which lower designates a carbon content of one to four carbon atoms.

2. A compound according to claim 1 wherein R represents the group having the formula R-X-- and one of R and R is lower alkyl and the other is hydrogen.

3. A compound according to claim 1 having the formula wherein R is lower alkyl; X is O-- or S; A is lower alkanoyl, lower alkoxycarbonyl, or benzoyl; R and R each is hydrogen or methyl; R is hydrogen or lower alkyl; and one of 'R and R is hydrogen.

4. A compound according to claim 3 wherein RX is methylthio or ethylthio; A is acetyl or propionyl; R is methyl; and R and R is hydrogen. 

2. A compound according to claim 1 wherein R represents the group having the formula R4-X- and one of R1 and R2 is lower alkyl and the other is hydrogen.
 3. A compound according to claim 1 having the formula wherein R4 is lower alkyl; X is -O- or -S-; A is lower alkanoyl, lower alkoxycarbonyl, or benzoyl; R1 and R3 each is hydrogen or methyl; R2 is hydrogen or lower alkyl; and one of R1 and R2 is hydrogen.
 4. A compound according to claim 3 wherein R4-X- is methylthio or ethylthio; A is acetyl or propionyl; R1 is methyl; and R2 and R3 is hydrogen. 